Color photographic light-sensitive elements with both colored and colorless color couplers

ABSTRACT

A photographic element containing diffusion resisting 4-azopyrazolone and a colorless phenol or Alpha -naphthol derivative in the silver halide layer.

United States Patent 1 Oishi et al.

[73] Assignee: Fuji Photo Film Co., Ltd.,

Ashigara-shi, Kanagawa, Japan [22] Filed: Mar. 7, 1972 [21] Appl. No.: 232,518

Related U.S. Application Data [63] Continuation-in-part of Ser. N6. 824,294, May 13,

1969, abandoned.

[30] Foreign Application Priority Data May 13, 1968 Japan 43-32024 [52] U.S. Cl 96/55, 96/9, 96/56.1,

[451 Feb. 5, 1974 [51] Int. Cl. G03c 7/00 [58] Field of Search 96/9, 100, 55

[56] References Cited UNITED STATES PATENTS 2,852,370 9/1958 Whitmore 96/9 3,005,712 10/1961 Saunderset al. 96/9 3,476,564 11/1969 Mariani et al. 96/9 3,671,257 6/1972 Otto et al 96/9 Primary Examiner-J. Travis Brown Assistant Examiner-Richard L. Schilling Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A photographic element containing diffusion resisting 4-azo-pyrazolone and a colorless phenol 0r a-naphthol derivative in the silver halide layer.

8 Claims, No Drawings 1 I COLOR PHOTOGRAPHIC LIGHT-SENSITIVE ELEMENTS WITH BOTH COLORED AND COLORLESS COLOR COUPLERS CROSS-REFERENCE TO RELATED APPLICATION This is a continuation-in-part application of copending application, Ser. No. 824,294, filed May 13, 1969, now abandoned.

BACKGROUND OF THE INVENTION mation transfer, for example-projection slides for commercial displays, and educational illustrations. These photographs have generally been prepared either from monochromatic light-sensitive materials or from colorphotographic materials.

While the image patterns in monochromatic photographs consist of contrast between black and white, they consist of contrast between colors in color photographs. For the purpose of information transfer, color photographs are preferred to the monochromatic ones because contrast between colors attracts the attention of audience more strongly than contrast between black and white.

The preparation of color photographs, especially the preparation of the original patterns, is tedius and timeconsuming. The originals must be drawn on colored paper with a paint or a color. Further, color photographs prepared by conventional systems do not have enough color saturation for displays or illustrations.

SUMMARY OF THE INVENTION Therefore, an Object of the present invention is to provide a color photographic light-sensitive element capable of giving image patterns of high contrast and good color saturation.

single silver halide emulsion layer on a support to form a color photographic light-sensitive element.

That is, the first compound (hereinafter coupler A") is a yellow dye that mainly absorbs light having 5 wave lengths of 400 500 m. ,u. and reacts with the ox- Another object of the present invention is to provide idation product of a p-phenylene diamine type color developer formed by development to provide a magenta dye that mainly absorbs light having wavelengths of 500 600 m. t. g

The second compound (hereinafter coupler B) employed as a color coupler in this invention, originally colorless, is converted into a cyan dye that mainly absorbs light having-wave lengths of 600 700 m. ,uby reaction with the oxidation product of a color developer.

"oETAILEDbEscRIPrION OF THE INVENTION Coupler A, used in the present invention, can be selected from pyrazolone compounds, taking into consideration the requirements for spectral absorption characteristics as a yellow dye and spectral absorption characteristics as a magenta dye after thecoupling thereof with the aforesaid oxidation product. The compounds are represented by the following general formula:

wherein-R man, eacifiefirsefii's'an aryl group, a substituted aryl group, a heterocylic group, or substituted heterocyclic group, R represents an unsubstituted or substituted aryl group, and unsubstituted or substituted alkyl group, or an amino group, an acylamino group, an ureido group or a sulfonylamino group each bonded to an unsubstituted or substituted alkyl or aryl group, and at least one of R or R represents ananti-diffusion or ballast group or more than eight carbonatoms In the preferred form of coupler A of the present invention, R is phenyl or substituted phenyl, R is acylamino or ureido, of about eight to 30 carbon atoms, and R is aryl or substituted aryl.

As described above, it is necessary that coupler A have an anti-diffusion group (or a ballast group having more than eight carbon atoms in the molecule at the R or R position to prevent the coupler from being crystallized in the emulsion layer, from diffusing into the other layers, and from being dissolved in a developing solution. As coupler A, pyrazolone type colored couplers usually employed for automasking method can be utilized. These compounds are well known and the practical examples of such compounds particularly suitable for use in the present invention are as follows:

formula 1 NHC OCHCiaHar HaCOOH These compounds may be prepared by a well known process, i.e., by the coupling reaction of a pyrazolone compound and an aryldiazonium compound or a heterocyclic diazonium compound. Practical examples of the preparation of the aforesaid couplers are described in, e.g., Vittum et al.; Journal of American Chemical Society; Vol. 72, 1533-1536, Belgian Patent No. 675,259 U.S. Pat. No. 3,127,269, etc. Also, many of the 4-azopyrazolone compounds shown in these publications can be employed as coupler A in the present invention.

Coupler 13, used in this invention, may be selected from colorless compounds capable of providing cyan dyes having main absorption regions at 600 700 m. u. by the reaction thereof with the oxidation product of a color developer. Coupler B may be selected from compounds having wide structural ranges, since the spectral absorption of the cyan dye formed by coupler B and the oxidation product of the color developer overlaps the spectral absorption of the magenta dye formed from coupler A. Like coupler A, Coupler B has a diffusion resistant or ballasting group of at least 8 carbon atoms. I

For these purposes, phenol derivatives or anaphthol derivatives having a ballasting group of at least 8 carbon atoms are useful. Compounds particularly useful in the present invention are the derivatives represented by general formula (II) and general formula (Ill) below:

formula (II) formula. (III) drogen atom, a halogen atom, a lower alkyl group, or

a lower alkoxy group, X represents an atom ora residual group capable of being split off in the coupling reaction such as a hydrogen atom, a halogen atom or a sulfone group, with at least one of R, and R and at least one of R and R having at least eight carbon atom s.

In the preferred form of coupler B of the present invention, R is hydrogen or alkyl, R is alkyl. substituted alkyl, or substituted aryl, with at least one of R and R being a group of abouteight to 30 carbon atoms, Ris hydrogen, R, is alkyl or substituted alkyl, with at least one of R and R being a group of about eight to 30 carbon atoms, and R and R are 6-chloro and S-alkyl. wherein there are about one to live carbon atoms in the alkyl group.

As described above, coupler B must have a ballast group for fixing the coupler in the emulsion layer. The

typical examples of coupler B represented by aforesaid general formulae are as shown below.

The amount of the diffusion resistant pyrazolone compounds, coupler A, incorporated into the emulsion 0 ONHCizI-In (M) H OH we corrmcmn-o-Q-ommo k/ 1103) fl OONHCnHar C ONHCHICHINHO O C HG mHaa i OaH /CH3 CON CHQCHQCN CON\ o1 NHGOCHO- C5Hn(t) 2H5 A CH3. BHII) z o). l l.. OH

I CONH-Q-CONHCuHu 2 0H 1) omomcN CON 0012 0 ONHZH-Q-OCnHzs (23) OII NHCONH C isHzr ifiifllllifl; q earn; 7

OH N

\ soiNa N S(i)aH l5H3l I 01 NHCONHC H The above compounds and other phenols and a-naphthols which can be used in this invention as coupler B are shown in W. Plez; Mitteilung aus Agfa A.G. Leverkusen"; Vol. 3, pages l56-l74 and they may be prepared by the processes illustrated in Kimura and Yoshida; Yuki Gosei Kagaku Kyokaishi (Journal of Organo Synthetic Chemistry," Vol. 23, No. lll, all herein incorporated by reference.

When a color photographic light-sensitive element having one emulsion layer containing coupler A and coupler B is, after light-exposure, processed in a usual color developer containing a p-phenylenediamine type developing agent, no coupling reaction occurs in the unexposed areas of the emulsion layer and the areas assume a yellow color due to the absorption of mainly 400 500 m. a. wave length light caused by coupler A. On the other hand, coupler A and coupler B both are subjected'to the coupling reaction in the exposed areas of the emulsion layer to provide a magneta dye and a cyan dye respectively. As the result thereof, the exposed areas mainly absorb light of 500 700 m. a. in wave length and assume a blue color. The yellow (unexposed) areas and the blue (exposed) areas of the layer show clear and strong color contrast.

Such remarkable color contrast can give a far stronger impression than contrast between black and white or contrast between colors obtained by conventional processes. Therefore,- the color photograph obtained by using the color photographic light-sensitive element of the present invention is very useful for attractively displaying figures or tables. For example, the photograph can be particularly usefully employed as projection slides for education, as media for presenting technical data to the audience, or as displays for commercial purposes.

The color photographic light-sensitive element of the present invention provides the aforesaid image having a high color contrast by a simple procedure. That is,

usual black and white line patterns or continuous images may be utilized as the original. For example, patterns obtained by drawing on a white paper with a black ink or an ink stick or an image obtained by printing on a white paper in a black ink maybe utilized.

Since the couplers incorporated in the emulsion layer of the color photographic light-sensitive element of the present invention are substantially completely con- .11..- verted into dyes in the exposed areas by exposure and development, the blue hues obtained can be controlled, with good reproducibility, by the amount of coupler used, and clear and distinct contrast between the blue areas and the yellow areas can always be obtained.

Moreover, by incorporating a small amount of a colorless magenta yielding coupler in the emulsion layer of the light-sensitive element of the present invention, as well as couplers B and A, mentioned above, the color tone in blue can be delicately controlled.

Both coupler A and coupler B may be employed alone or may be used as a mixture of two or more compounds shown above.

As mentioned above, coupler A and B have ballast groups, for incorporating the coupler in a emulsion. Conventional techniques, such as methods wherein the coupler is added as an aqueous solution thereof, or a solution thereof in an oil (coupler'solvent), may be employed.

Any coventional silver halide emulsion, both those which are optically sensitized and those which are not, may be used in the present invention. However, since blue light having wave lengths of 400 500 m. a. is absorbed by coupler A it is preferable to use a green and- /or' red sensitized emulsion to compensate for the loss of blue-sensitivity of the emulsion. v The photographic light-sensitive element of this invention may have, on a support, besides the aforesaid silver halide emulsion layer containing the couplers, subsidiary layers such as an antihalation layer and a protective layer.

Instead of coupler A used in the present invention, an a-naphtholcompound having an aryl azo group or a heterocyclic azo group at the 4th carbon atom may be employed together with the colorless magenta coupler, but the yellow color of such a compound has red overtones, and thus, color contrast between the yellow color and a blue color obtained by the coupling thereof is inferior to the color contrast obtained by using coupler A according to the present invention.

The invention will further be explained by the following examples.

EXAMPLE 1 0.5 g. of l-(2', 4, 6', trichlorophenyl) -3-[3- (2", 4"-di-tert-amylphenoxy-acetamido benzamido)-4-(4'- metho'xy-phenyl-azo)]-5-pyrazolone and 1.0 g. of 1- hydroxy-N- n-dodecyl-Z-haphthamide were dissolved in a mixed solvent of 3 ml. of tri-o-cresyl phosphate and 2ml. of ethyl acetate. The resulting solution was dispersed in 15 ml. of an aqueous 10 percent gelatin solution containing 1 ml. of an aqueous 5 percent solution.

of sodium n-dodecyl-benzene sulfonate. The coupler dispersion thus prepared was added to 100 g. of a red-' sensitive emulsion containing 7.0 g. of gelatin and 3.3 X moles of silver chlorobromide. This silver halide emulsion was applied to a triacetyl cellulose film having an antihalation layer applied thereto, so that the dry thickness thereof would become 5 microns. The product was then dried to provide a sample film.

a. The light-sensitive film thus prepared was loaded in a camera and exposed to an original drawn on a white paper with black ink and then developed for 14 minutes at 2l-C in a color developer having the following composition:

Water I liter Benzyl alcohol 4.0 ml Sodium hexametaphosphate 2.0 g. Sodium sulfite (anhydrous) 2.0 g. 4-Amino-N-ethyl-N-(B-methanesulfonamidoethyl)-m- I toluidinc sulfate 5.0 g. Potassium bromide 1.0 g. Sodium carbonate monohydrate 50 g.

The pH of the developer was then adjusted to 10.8 with an aqueous 10 percent sodium hydroxide solution.

- The developed photographic film was fixed in an acid fixing solution, washed with water, bleached in a bleaching solution containing a ferricyanide and potassium bromide, washed with water, fixed again, washed with water, and then dried. When the resulting slide was shown by means of a projector, a color image having a high color contrast was obtained in which the blue areas corresponded to the white areas of the original and the yellow areas to the black figure areas.

b. A black-and-white negative was prepared from the original used in the experiment a. Thereafter, the aforesaid sample film was exposed through the negative film. The sample film was then subjected to the color developement as in experiment a to provide a color photograph, from which a slide was prepared. When theslide was shown by means of a projector, a figure was obtained wherein the white areas of the original corresponded to the yellow areas of the slide and the black line or character corresponded to the blue areas.

c. A black-and-white original was directly photographed as in experiment a on the sample film prepared above, and the film was developed for 5 minutes at 20C, in a black-and-white developer having the following composition:

Water N-methyl-p-aminophenol sulfate Sodium sulfite (anhydrous) Sodium carbonate monohydrate Potassium bromide Citric acid 1 liter After washing with water, the sample was uniformly exposed to light and then subjected to the' series of procedures mentioned in experiment a to provide a color slide. In the color slide, the white portions of the original corresponded to the yellow portions of the slide and the black figure portions to the blue portions.

acidsulfonic acid-N-n-octadecyl-Z-naphthamide were dissolved in 10 ml. of water containing 0.06 g. of sodium hydroxide and the resulting solution was added to g. of a green-sensitive emulsion containing 5.0 g. of gelatin and 5.4 X 10 mole of silver iodobromide. To provide a sample film, the silver halide emulsion thus obtained was applied to a triacetyl cellulose film having applied thereto an antihalation layer, so that the thickness of the dry layer was 5 microns.

a. The black and white negative film obtained in experiment b of Example 1 was printed by enlarging on the sample film obtained in Example 2 by using an optical enlarger. The sample film was then subjected to the color development procedures as mentioned in experiment a of Example 1, to provide a color photograph. When the photograph was attached to glass plate and the glass plate was illuminated by fluorescent light from the back side a beautiful color figure was obtained.

b. The sample film prepared in Example 2 was inserted between a flurorescence-sensitizing plate and the chest of a human body was photographed by X rays. Then the sample film was subjected to the color development procedures as stated in experiment a of Example I to provide a color photograph in which the blue portions corresponded to the areas strongly exposed by the X-rays and the yellow portions to the areas weakly exposed by the X-rays.

What is claimed is:

l. A color photographic light-sensitive element comprising a support, and a single silver halide emulsion layer containing color couplers, said couplers consisting essentially of a diffusion resisting 4-azo-pyrazolone compoundof the formula:

wherein R, and R each represents a member selected from the group consisting of aryl and heterocyclic, and R represents a member selected from the group consisting of alkyl, aryl, amino, acylamino, ureido, and sulfonylamino groups, wherein said amino, acylamino, ureido and sulfon'ylamino groups contain a member selected from the group consisting of alkyl, and aryl, one

of said R 'or R being a ballast group of more than eight carbon atoms, and a compound selected from the group consisting of diffusion resisting colorless phenols and diffusion resisting colorless a-naphthol derivatives, said diffusion resisting colorless phenol being repre sented by the following formula:

wherein R is a member selected from the group consisting of hydrogen and alkyl, R represents a member selected from the group consisting of alkyl and aryl, R

and R each represents a member selected from the group consisting of hydrogen, halogen, lower alkyl and lower alkoxy groups,-and X represents a member selected from the group consisting of hydrogen, halogen, and sulfone groups and said a-naphthol derivative being represented by the following formula:

wherein R represents a member selected from the group consisting of hydrogen and alkyl, R represents a member selected from the group consisting of alkyl and aryl, and X represents a member selected from the group consisting of hydrogen, halogen and sulfone groups, at least one of R and R having from eight to 30 carbon atoms and at least one of R5 and R7 having from eight to 30 carbon atoms.

2. The color-photographic light-sensitive element as claimed in claim 1, wherein said element additionally contains an anti-halation layer.

3. The color photographic light-sensitive element as claimed in claim 1, wherein R is a phenyl group, R is selected from the group consisting of acylamino and ureido groups and has from eight to 30 carbon atoms, and R is an aryl group.

4. The color photographic light-sensitive element as claimed in claim 1, wherein R is hydrogen, R is an aryl' group of from eight to 30 carbon atoms, R is 6-chloro and R is a S-alkyl group of one to five carbon atoms.

5. A process for preparing a photographic image having high blue to yellow contrast comprising imagewise exposing to light a photographic light-sensitive element comprising a support and a single silver halide emulsion layer containing color couplers, said couplers consisting essentially of:

a. a diffusion resisting 4-aZo-pyrazolone compound of the formula:

i l-00m wherein R is a member selected from the group consisting of hydrogen and alkyl, R represents a member selected from the group consisting of alkyl and aryl, R

and R each represents a member selected from the .group consisting of hydrogen, halogen, lower alkyl and lower alkoxy groups, and X represents a member selected from the group consisting of hydrogen, halogen,

and sulfone groups and a diffusion resisting a-naphthol derivative represented by the following formula:

oil

CON

wherein R represents a member selected from the group consisting of hydrogen and alkyl, R represents a member selected from the group consisting of alkyl and aryl, and X represents a member selected from the from eight to 30 carbon atoms, and developing said element in a developer containing a p-phenylenediamine type developer to form silver and dye images and removing said silver image to leave said dye image.

6. The process of claim 5, where said R is a phenyl group, R is a member selected from the group consisting of an acylamino group and ureido group having from eight to 30 carbon atoms, and R is an aryl group.

7. The process of claim 5, wherein said R is hydrogen, R is an aryl group, R is 6-chloro, and R is a 5- alkyl group having from one to five carbon atoms.

8. The process of claim 5, wherein said element additionally contains an anti-halation layer. 

2. The color-photographic light-sensitive element as claimed in claim 1, wherein said element additionally contains an anti-halation layer.
 3. The color photographic light-sensitive element as claimed in claim 1, wherein R1 is a phenyl group, R2 is selected from the group consisting of acylamino and ureido groups and has from eight to 30 carbon atoms, and R3 is an aryl group.
 4. The color photographic light-sensitive element as claimed in claim 1, wherein R6 is hydrogen, R7 is an aryl group of from eight to 30 carbon atoms, R8 is 6-chloro and R9 is a 5-alkyl group of one to five carbon atoms.
 5. A process for preparing a photographic image having high blue to yellow contrast comprising imagewise exposing to light a photographic light-sensitive element comprising a support and a single silver halide emulsion layer containing color couplers, said couplers consisting essentially of: a. a diffusion resisting 4-azo-pyrazolone compound of the formula:
 6. The process of claim 5, where said R1 is a phenyl group, R2 is a member selected from the group consisting of an acylamino group and ureido group having from eight to 30 carbon atoms, and R3 is an aryl group.
 7. The process of claim 5, wherein said R6 is hydrogen, R7 is an aryl group, R8 is 6-chloro, and R9 is a 5-alkyl group having from one to five carbon atoms.
 8. The process of claim 5, wherein said element additionally contains an anti-halation layer. 